Isocyanate adducts and preparation thereof

ABSTRACT

(3) MIXTURES OF (1) AND (2), WHEREIN R is alkyl having a maximum of 4 carbon atoms and R1 is selected from the group consisting of mono- and dihalosubstituted phenyl and mononitrosubstituted phenyl.   Phytotoxic and soil sterilant compounds of the formula (CH2 NR)3(R1NCO)2 and having either of the following structures:

United States Patent [72] Inventor JohnP.Chupp Kirkwood, Mo.

I21 1 Appl No. 623,541

[22] Filed Mar. 16, 1967 [45) Patented Sept. 28, 1971 [73] Assignee Monsanto Company St. Louis, Mo.

[54] ISOCYANATE ADDUCTS AND PREPARATION THEREOF 1 1 Claims, No Drawings I52] U.S. Cl 260/2393, 71/92, 260/453 [51] 1nt.C1 A0ln 9/22, C07d 55/64 [50] Field of Search 260/453 A, 239.3

[56] References Cited UNITED STATES PATENTS 3,126,404 3/1964 Flynn et al. 260/453 3,444,231 5/1969 Merz 260/453 OTHER REFERENCES Lange: .I. Am. Chem. Soc., Vol. 48, pp. 2440- 2444 (1926). Clemens: J. Org. Chem., Vol. 26, pp. 767- 769 1961 Primary Examiner-Charles B. Parker Assistant Examiner-Dolph H. Terrence AttorneysNeal E. Willis, John J. Hcnschke, Jr. and David D.

Ccntola ABSTRACT: Phytotoxic and soil sterilant compounds of the formula (CH N-R);,(R'NCO) and having either of the following structures:

wherein R is alkyl having a maximum 014 carbon atoms and R is selected from the group consisting of monoand dihalosubstituted phenyl and mononitrosubstitutcd phenyl.

lSOt, YANATE ADDUCTS AND PREPARATION THEREOF Organic isocyanates are known to undergo addition and polymerization reactions to yield a wide variety of products. The alcoholysis and aminonolysis of isocyanates to yield urethans and substituted areas is well known. The products are frequently solids and are used to identify the corresponding alcohol or amine.

It has now been found that aryl isocyanates react with azomethines (or their trimers) to yield solid adducts which have phytotoxic activity.

lt is an object of this invention to provide a novel process for the preparation ofisocyanate-azomethine adducts.

It is a further object of this invention to provide a process for the preparation of novel aryl isocyanate-azomethine adducts.

It is a further object of this invention to utilize isocyanateazomethine adducts as herbicides.

Further objects. aspects and advantages of the invention will be apparent from the description which follows.

Briefly, this invention provides a process for the preparation of novel isocyanate-azomethine adducts by reacting an azomethine (or its trimer) with an aryl isocyanate in an approximate temperature range of O"5O C. The reaction proceeds according to the following equation:

wherein R an group havirig a maximum of 4 carbon atoms and R is selected from the group consisting of halosubstituted phenyl and nitrosubstituted phenyl.

The term adduct as used herein is the chemical addition product formed from the reactants. ltis a new compound having a separate entity than the reactants. Therefore. the terms adduct and -compounds will be used interchangeably.

As seen in the equation above the molar ratio of azomethine to isocyanate is preferably about 3:2. This ratio yields an adduct (l) which is essentially uncontaminated with either ofthe starting compounds. This optimum mole ratio was determined by infrared and nuclear magnetic resonance studies of the reaction medium in which various ratios of isocyanate and azomethine were reacted. The presence of the NCO band at 4.5 micron (a) in the infrared was indicative of the presence of unreacted isocyanate in the medium. The presence of unreactive azomethine appeared in the nuclear magnetic resonance spectra of the reaction medium.

When 2 moles of azomethine per mole of isocyanate are reacted. the reaction medium was found, by the above analysis. to contain unreacted azomethine and the absence of any measurable amount of unreacted isocyanate.

Changing the molar ratio of lzl shows by analysis that the isocyanate is in excess and that no measurable amount of azomethine is present.

The reaction of 3 moles of azomethine per 2 moles of isocyanate yielded the desired product without either unreacted isocyanate or unreacted azomethine being detected in the reaction medium. This. therefore, shows that the adducts con sist of 3 moles of azomethine per 2 moles of isocyanate. This was confirmed by infrared. nuclear magnetic resonance. molecular weight and elemental analysis ofthe adduct.

It is apparent from the above description that some adduct is formed regardless ofthe proportions of reactants used in the process. In order to minimize the requirements of separation of the desired adduct from the reaction mixture, it is preferred to use an approximate molar ratio of 3:2 (azomethine:isocyanate).

In the preparation of the adducts, the reactants are normally dissolved in an organic solvent. such as pentane. and combined. preferably at temperatures in the approximate range of 50 C. The reaction mixture is then maintained for an extended period of time. about 2 to 4 days. at approximately room temperature. The product. which separates from the sol vent as a solid. is separated and triturated with a suitable solvent. e.g. diethyl ether. and the solvent removed, preferably under reduced pressure at approximately room temperature.

Other solvents, such as aliphatic and aromatic hydrocarbons. ethers and the like. can be used as the reaction medium. These solvents include, but are not limited to. pentane. hexane, heptane, benzene. cyclohexane, toluene. methyl ethyl 5 ether. diethyl ether. and isopropyl ether. Preferred solvents are those in which the adduct is insoluble. both the azomethine and isocyanate are soluble. and which can be easily removed under reduced pressure at about room temperatures. Aromatic hydrocarbons can be used. but since they usually have a high solubility for the product and are difficult to remove from the product. aliphatic hydrocarbons are generally preferred as the reaction medium.

The reaction temperature is preferably maintained between about 0 and about 50 C., but temperatures above the below this rangecan be employed. Above about 50 C.. the formation of the desired product is hindered and the yield. which normally is essentially quantitative. appreciably decreases.

The isocyanate-azomethine adduct has been assigned a generic configuration ll X R l l 1 N XN N-R wherein X and X is either R or R and Y and Y is either H. or oxygen; R and R are as previously defined; provided that when X is R. then X is R. Y is H and Y is oxygen (colitpound Ill); and further provided that when X is R. then X is R; Y is oxygen and Y is H (compound IV).

This configuration is based on infrared. nuclear magnetic resonance. molecular weight. physical properties. elemental analysis and experimental reaction data.

The adduct formed by the process of this invention is either compound II], compound IV or a mixture of the two com- These compounds, lll and IV differ in the position of the isocyanate groups, which are adjacent groups in formula IV and separated by an azomethine group in formula III. Both formulas Ill and W satisfy the molecular weight and spectral data. Nuclear magnetic resonance data show that all N-methyl groups and methylene groups are nonequivalent. which would be expected from both formulas.

ture used in the examples and throughout the specification is based on'thc structure of'formula lll.

EXAMPLEJ Preparation of l ,5 -Bis-( 3,4-dichlorophenyl)-hexahydro- 3,7,9-triethyll ,3,4,7,9-pentazccine-2,6-( lH,5H)-dione is according to the following procedure:

Trimeric N-cthyl azomethine l ,3 ,S-tricthylhcxahydrotriazine) (0.0367 mole, 6,27 g.) was dissolved in about 50 ml. dry pentane and then added, with stirring, to a clear fil tered solution of 0.0734 mole (l3.8 g.) of 3,4-diehlorophcnylisocyanate dissolved in about I ml. of dry pentane. An ex othermic reaction occurred upon addition of the azomethine. Following the addition the reaction flask was sealed and allowed to stand at room temperature (about 25 C.) for 2 days. The pentane solution was then decanted and the residue pulverized to a fine white powder, yield 16.2 g. This powder was then triturated with about 50 ml. dry diethyl ether, the ether removed and the residue vacuum stripped of solvent at room temperatures to yield l3.3 g. of a dry white solid, m.p. l09l l2.5 C. (decomposition), C H -,Cl N .,O

Analysis Calculated Found Cl 25.9l 25.94

Molecular weight determination was an osometric determina tion in chloroform. Infrared spectra had a strong carbonyl bond at 6.0-6.1 a. Nuclear magnetic resonance spectra were The procedure of Example 1 was repeated, with the exception that dry diethyl ether was used as the solvent in place of dry pentane, to yield 1,5-Bis(3,4-dichlorophenyl) hexahydro- 3,7,9-triethyl-l,3,5,7,9-pentazecine-2,6-(1H,5H)-dione.

EXAMPLE 3 The procedure of Example 1 was repeated using trimeric N- methyl azomethine (l,3,5-trimethyl hexahydrotriazine) in place of the trimeric N-ethyl azomethine, to yield l,5Bis(3,4- dichlorophenyl) hexahydro-3 ,7,9-trimethyll ,3 ,5,7,9-pentazine-2,6-( lH,5H)-dione, C H ,Cl N O m.p. lOl-l 12 C. (decomposition). Analysis: Calculated: N=l 3.87; Cl=28.08 M.W.=505; Found: N=l 3.33; Cl=27.58; M.W.=5l2. Molecular Weight determination was an Osometric determination in benzene.

EXAMPLE 4 The procedure of Example I was repeated using 4- nitrophcnylisocyanatc in place of 3,4-dichlorophenylisocyanate to yield l,5-Bis(4-nitrophcnyl)-hcxahydro-3,7,9- triethyl-l ,3,5,7,9-pentazecine-2,6( lH,5H)-dione.

EXAMPLES The procedure of Example 1 was repeated using 3 chlorophenylisocyanate in place of 3,4-dichlorophenylisocyanate to yield l,S-Bis(3-chlorophenyl)hcxahydro-3,7,9- triethyl-l ,3,5,7,9-pentaxecinc 2,6-( lH,5H )-dione, H- Cl N 0 m.p. 97-l()4 C. (decomposition). Analysis: Calculated: N=l6.()6, Cl=l6.2o; M.W.=436; Found: N=l5.84, (1 16.20; M.W.=43b. Molecular weight determination was an (isometric determination in chloroform.

The compounds of this invention have been found to exhibit soil sterilant and herbicidal activity. Herbicidal activity has been shown in both the preemergent and postemergent state, that is, the application of an effective amount of the compounds of this invention to seeds, emerging seedlings, the roots or above-ground portion of established vegetation, controls or modifies the growth of, germinated seeds, emerging seedlings and established vegetation.

The active ingredient can be applied alone or in combination with a material referred to in the art as a herbicidal adjuvant in liquid or solid form. The herbicidal compositions of this invention are prepared by admixing the active ingredients with an adjuvant which includes diluents, solid or liquid extenders, carriers and conditioning agents to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions and aqueous dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely divided particulate solid, a solvent liquid of organic origin, water, a wetting agent, dispersing agent, an emulsifying agent or any suitable combination of these.

Herbicidal composition" as used herein and in the appended claims includes not only compositions in a suitable form for application but also concentrated compositions which require dilution or extension with a suitable quantity of liquid or solid adjuvant prior to application.

The following examples illustrate the herbicidal activity of the adduct:

EXAMPLE 6 Postemergent Herbicidal Activity An aluminum pan approximately 9 inches X l3 inches X 2 inches is filled with top soil and the soil compacted to within three-eighths inch from the top of the pan. A predetermined number of seeds of the following plant species: cotton, corn, soybeans, cocklebur, crab grass, lambsquarter, wild oats, smartweed, brome, barnyard grass, sugar beet, wheat, rice and cofTeeweed, are placed on the top of the soil and the pans filled with top soil and leveled. The pans are watered through apertures in the bottom of the pans and are then maintained under ordinary greenhouse conditions of sunlight and water for 14 days.

The ingredient to be tested is applied to the 14 day old plants in spray form. The herbicidal sprays are acetone-water solutions containing 0.1 percent and 0.02 percent by weight of active ingredient and 0.4 ml. of a 3:1 cyclohexanol emulsifier (butyl-amine salt of dodecylbenzenesulfonic acid 35 percent; tall oil-ethylene oxide condensate 65 percent) solution and are applied at a rate of 2 and 0.4 pounds of active ingredient per acre of land, respectivelyv The treated plants are placed in a greenhouse and the effects are observed and recorded after 28 daysv The results are tabulated, as percent control, in Table l. Identification ofthe plants used is as follows:

A-Cotton H Smartwced B-(orn I-Brorne Grass C Soybean K W Barnyard Grass D-Cocklehur L-Sugur Beet ELrab (truss M Wheat F- Lambsquurter ORice (JWild Oat P-Coffee Weed TABLE I.-POST-EWERGENT HERBICIDAL ACTIVITY Rate, Compound lbs/acre A I; C D E F G 1 I I J K I M N U l (1) 2 60 100 100 35 100 31] 16 mo 100 30 45 40 1M) 0 4 0 0 0 0 10 1m 0 u 0 100 I m H 5 0 I5 -2 l 2 10 0 10 (l 55 0 l5 0 2!) 0 ll 5 21) ll) .55 i 4 0 t) t] l) l) (l 0 ll 0 ll ll 0 l) i) 0 U (3) 2 0 0 ll (1 .25 ill) 0 15 it (ll) l) U 5 0 ll 0, 4 0 0 o u n n n 0 u u 0 l5 0 o o 0 (4) 2 ll) 25 11] 25 101) 50 (i0 ll) J5 35 7h 15 15 15 5X 0, 4 0 0 0 0 0 (so 0 u u 100 u an 0 n o 10 NOTE (1) =1,5-bis (3,4'dieh1oropheny1-)huxahydro-3,7,tJ-trlmnthyH ,d,5,7, J-politnzuc1no--,6-(1 ll,6] l drone. 2 =1 5 b1 (3chl0ropheny1-) hexnhydro-3,7,ll-trirnothyl-1,3,5,7,ll-pnntnzuclne-2,6-(1ll,5ll) (hone. 3)=1'5-bis (3,4-dichlorophenyl-) hexahydro-3,7,9,-tnothyl-1,3,5,7,ttpontuzeeino-2,o-(1l1.511) (110110. (4) =115-bis (4-eh1orophenyb) hexahydro-3,7,0-trimethyl-1,3,5,7,lpentazeetne-2,6-(11I,5l1) dlono.

EXAMPLE 7 Preemergent Herbicidal Activity An aluminum pan approximately 9 inches X 6 inches X 3 inches, is filled with a good grade of top soil and the soil compacted to within three-eighths inch from the top of the pan. A predetermined number of seeds of the following plant species: morning glory, wild oat, brome, rye grass, radish, sugar beet, foxtail, crab grass, pigweed, soybean, wild buckwheat, tomato and sorghum are placed on the top of the soil and the pans filled with top soil and leveled. The herbicidal composition is applied by spraying the surface of the top layer of soil, prior to watering the seeds, until a rate of 10 pounds of active ingredient per acre has been applied to the soil surface. The pans are watered through apertures in the bottom of the pans, and are then maintained under ordinary greenhouse conditions of sunlight and water for 14 days.

The plants are observed at the end of 14 days and the results recorded. The herbicidal activity index is based on the average percent germination of each seed lot.

The preemergent herbicidal activity index used in Table II defined as follows:

Identification of the seeds used is as follows: A-Morning Glory HCrab Grass The compound identification is the same as in Table the compounds of this invention exhibit a selective preemergent herbicidal effect in addition to the residual effect which is advantageous for specific weed control in crops such as corn, cotton and soybean (Table III EXAMPLE 8 An aluminum pan, approximately 9 inches X 6 inches X 3 inches is filled with a good grade of top soil and the soil compacted to within three-eighths from the top of the pan. A predetermined number of seeds of the species listed in Table III are placed on the top of the soil and the pans filled with top soil and leveled. The herbicidal composition is mixed with the cover layer of soil in rates equivalent to 4, 2 and 1 pound per acre. The pans are watered through apertures in the bottom of the pan and then maintained under ordinary greenhouse conditions of sunlight and water.

The plants are observed at the end of i4 days or 28 days depending upon the rate of herbicidal application and the results recorded. The herbicidal activity index is based on the average percent germination of each seed lot, as described in Example 7.

ldentil'ication ofthe seeds used is as follows:

A-Cotton |Brome B-Corn JPigweed CSoybean K-Barnyard Grass DCocklebur L-Sugar Beet E-Crab Grass MWheat FLambsquartcr NVelvet Leaf GWild Oat O-Rice HSmartweed A P-Cnflee Weed Many herbicides are deficient in that they are rapidly dissipated or destroyed in the soil and, therefore, have little or no residual effect.

When such compounds are used for weed control in crops, multiple applications are required during the crop growing and harvesting periods to insure adequate weed control.

For applications requiring a soil sterilant effect, such as railroad right away where plant control over an extended period of time of several years is desired, these prior art herbicides TABLE II.PRE-EMERGENT HERBICIDAL ACTIVITY Rate, Compound lbs/acre A B C D E F G H I J K L M 10 2 3 2 3 2 3 3 3 3 0 3 3 3 1O 3 3 3 3 3 3 3 3 3 2 3 3 3 10 0 0 O 0 O 1 0 2 3 0 O 0 O 10 1 1 1 1 2 3 2 3 3 0 2 2 1 At concentrations less than 5 pounds preferably in the approximate range of 2 to 4 pounds per acre,

per acre, and 65 are applied in large quantities of 50 to pounds per acre.

It has been found that the compounds of this invention pos- TABLE III.PRE EMERGENT HERBICIDAL ACTIVITY Plants Rate, observed Compound lbs/acre A B C D E F G H I J K L M N O P after- Remarks 4 0 0 0.5 1.5 3 3 2 2.5 2 3 3 3 1. 5 2. 5 0.5 14 days. Average of 2 runs. (1) 2 0 0 0 o 2 a 0 0 0 3 2 2 0 0 1 2 28 days. D0.

No'rE.(1)=Adduet o13,4-dich1oropheny1isoeyanate and N-methylazomethine.

sess a residual effect when applied in relatively small amounts of to pounds per acre. This persistency permits the use of the compounds as soil sterilants for general weed control.

At concentrations less than 5 pounds per acre, and preferably in the approximate range of2 to 4 pounds per acre, the compounds of this invention exhibit a selective preemergent herbicidal effect which may be advantageously used for specific weed control in crops such as corn, cotton and soybean.

An example of the soil sterilant activity of the compounds of this invention for general weed control is illustrated by the following:

EXAM PLE 9 Metal pans, 9% inches x 5% inches X 2% inches, are filled, and compacted, to the top with air dry Memphis silt loam. The active ingredient is sprayed on the soil surface until a rate of 5 pounds per acre has been applied to the soil surface. The pans are then held dry for 3 weeks under greenhouse conditions. After the 3-week period, the top one-half inch of soil is removed and the appropriate plant species to be tested seeded. The top soil, which was removed, is mixed by hand and replaced over the seeds. The pans are then watered through the bottom of the pan and then maintained under normal greenhouse conditions, using su birrigation, for a period of 6 weeks. At the end of this period, the plants are observed for the effect of the active ingredients.

The pans will then be oven dried, the top one-half inch of the topsoil removed and the plants reseeded. The removed topsoil is mixed with the equivalent of 50 pounds per acre of nitrogen and the topsoil replaced. The pans are then watered, as before and maintained under normal greenhouse conditions, with subirrigation, for 6 weeks. At the end of this period, the plants are once again observed for the effect of the active ingredient.

The second cycle is repeated as long as three or more grasses or broadleafs or the nutsedge are controlled 75 percent or more by the original application.

The soil sterilant activity is reported in Table III as percent control. The compound used in Table IV is the adduct of 3,4- dichlorophenylisocyanatc and N-methylazomethine.

TABLE 1v SOIL STERILANT ACTlYl TY Cycles Plant 1 2 3 4 Pigwccd lOU I00 100 [00 Morning Glory (Ann) 95 95 90 Smartweed I00 100 85 30 Cocltclbur l00 7S Italian Rye Grass 100 I00 I00 90 Rye 60 I00 100 60 Sorghum 99 100 75 60 Ouackgrass I00 I00 90 I00 Nutsedgc (No.) 0 0 0 40 Results are in percent control.

Active ingredient-adduct of 3,4-dichlorophcnylisoeyanate and N-methylu'mmcthine applied to a rate of5 pounds per flCl'LI.

used to their greatest advantage in modifying the growth of plant systems in soil, preferred herbicidal compositions have been developed which comprises certain wettable powders, aqueous suspensions, dust formulations, granules, cmulsiiiable oils and solutions in solvents. These compositions can also contain, as a conditioning agent, one or more surface active agent in an amount sufficient to render a given Composition containing the active component readily dispcrsihle in water or in oil. The term surface-active agent includes wetting agents, dispersing agents, suspending agents, emulsifying agents and the like.

Surface-active agents which can be used in the herbicidal compositions are set out, for example, in Searle U.S. Pat. No. 2,426,417; Todd U.S. Pat. No. 2,655,447; Jones US. Pat. No. 2,412,510; or Lcnher US. Pat. No. 2,139,376. A detailed list of such agents is set forth in Detergents and Emulsifiers-Uo to-date I961 by J. W. McCutchcon, lnc., Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture; and Soap and Chemical Special ties" (Nov. I947) pages 1 et seq. The surface-active agents are generally employed at concentrations of about 1 to 15 parts by weight per [00 parts by weight of the herbicidal composition.

Powdered or dust herbicidal compositions are usually characterized by their free-flowing and rapid settling properties. They are dense, finely divided particulate compositions intended for application to the soil in a dry form. Dusts are primarily comprised of the active ingredient and a dense, freeflowing, finely divided particulate extender. For ease and convenience in manufacture, an inert absorptive grinding aid, such as natural clays, diatomaccous earth, synthetic minerals derived from silica, and the like may be used. Preferred grind ing aids include, but is not limited to, attapulgitc clay, diatomaceous earth, synthetic fine silica, synthetic calcium silicate and synthetic magnesium silicates. Wetting agents, as hereinafter described can also be incorporated in the dust composition.

The inert solid extenders, for use in dusts, are of vegetable and mineral origin and possess relatively low surface areas and poor liquid absorption. Extenders used include, but is not limited to, micaceous tales, illitic clay, pyrophyllite, dense kaolin clays, ground calcium phosphate, rock dust and tobacco dust.

Dusts usually contain from about 0.5 to 99 parts active in gredicnt, 0 to 50 parts grinding aid, 0 to 3 parts wetting agent and 1 to 99.5 parts dense solid extender, all parts being by weight based on the total weight of the dust.

Wettable powder herbicidal compositions are similar to the powder or dust composition. A wettable herbicidal powder is a water-dispersible composition containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents.

The preferred wetting agent includes alkyl benzene sulfonates, alkyl naphthalene sulfonate, sulfated fatty alcohols, sulfated fatty amines or sulfated fatty acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylinic glycols and the like. Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium liquor sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonates, polymethylene bis-naphthalenesulfonate and sodium N- methyl-N-(long chain acid) taurates.

Inert solid extenders for use in wettable powder compositions are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. The extenders include, but are not limited to kaolinites, attapulgite clay and synthetic magnesium silicate.

The wettable powder compositions of this invention usually contain from about 5 to about parts of active ingredient, from about 0.25 to about 3.0 parts of wetting agent, from about 0.25 to about 7 parts of dispersant and from about 4.5 to about 94.5 parts of inert solid extender, all parts being by weight of the total composition. A corrosion inhibitor and/or antifoaming agent may be substituted, where needed, for from about 0.1 to 2 parts by weight of the solid inert extender.

Aqueous suspensions are usually prepared by mixing together, in water, a water insoluble active ingredient with dispersing agents to obtain a concentrated slurry of very small and finely divided particles. This concentrate when diluted and sprayed provides a very uniform coverage.

Emulsifiable oils are usually solutions of the active in gredient in waterimmiscible solvents together with a surfac tant. The composition generally contains from about to 95 parts active ingredient, about I to parts surfactant and about 4 to 94 parts solvent, all parts being by weight based on the total weight of the composition. Solvents which are used in this composition includes, but is not limited to, hydrocarbons and water immiscible ethers, esters, ketones and the .like. The surfactant may be anionic, cationic or nonionic and includes alkyl aryl polyethoxy alcohols, alkyl and aklyl aryl polyether alcohols, polyethylene sorbitol or sorbitan fatty acid esters, polyethylene glycol fatty esters, amine salts of fatty alcohol sulfates, long chain alcohols and oil soluble petroleum sulfonates or mixtures thereof.

Granules are physically stable particulate compositions comprising an active ingredient adhering to or distributed through a basic matrix of an inert, finely divided particulate extender. Preferred extenders are the porous, absorptive, preformed particles such as the preformed and screened particulate, and the finely divided clays such as kaolin clays, hydrated attapulgite, illitic clay or bentonitic clays. These extenders are blended or sprayed with the active ingredient to form the granules, The mineral particles are usually in the size range of 10 to 100 mesh, with l4 to 80 mesh being preferred and to 40 mesh being he optimum size desired.

Granular compositions are comprised of about 005 to 30 parts by weight of active component per 1 part by weight of clay and about 0 to 0.05 parts by weight of wetting agent per l part by weight of clay.

The herbicidal and soil sterilant composition of this invention can include other additaments, such as, fertilizers, other phytotoxicants, pesticides and the like, used as adjuvants or in combination with any of the above-described adjuvants.

Phytotoxicants useful in combination with and as synergistic mixtures with the compounds of this invention include 2,4- dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and their salts, esters and amides; triazine derivatives, such as 2,4-bis(3- mcthoxypropylamino)-6-methylthio-s-triazine, 2-chloro-4- ethyl-amino-6-isopropylamino-s-triazine and 2-ethylamino-4- isopropylamin0-6-methylmercapto-striazine; urea derivatives, such as 3-(3,4-dichlorophenyl)-l,l-dimethyl urea and 3-(pchlorophenyl)-l,l-dimethyl urea, 3-(3,4-dichlorophenyl)-lmethyl-l-methoxy urea; acetanilides such as N-isopropyl-achloroacetanilide. N-ethyl-a-chloro-2-methylacetanilide and 2-tbutyl-2"-chloro-6-methyl acetanilide; acetamides, such as N,N-diallyl-a-ehloro-acetamide, N-(achloroacetyl) hexamethylene imine, N,N-diethyl-a-bromoacetamide and the like.

The compounds of this invention can be applied to the soil or plant system in any convenient fashion, such as mixing with the media, by applying to the surface of the soil in dry form and thereafter dragging or discing into the soil to the desired depth, by employing a liquid carrier to carry the ingredient into the soil, and the like. Application to plants can be by any of the conventional methods, such as powder dusters, boom and hand sprayers, spray clusters and the like.

The desired rate of application is as previously recited, however, quantities outside this range can be used. Optimum application rate is dependent upon, among others, soil texture, desired depth of ingredient in the soil, and the specific use of which applied, such as preor postherbicidal activity or soil sterilant. In soil applications, it is desirable that the active ingredients be distributed to a depth of at least 0.2 inches. One

skilled in the art can readily determine from this specification. including examples, the application rate for any specific situa- Aihile the illustrative embodiments of this invention have been described hercinbeforc with particularity, it will be un dcrstood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of the invention Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and description set forth herein but rather the claims be construed as enrmn passing all the features of patentable novelty which reside in the present invention including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

What is claimed is:

l. A compound of the formula and selected from the group consisting of wherein R is alkyl having a maximum of 4 carbon atoms and R' is selected from the group consisting of mononitrosubstituted phenyl and monoor dichlorosubstituted phenyl.

2. A compound in accordance with claim I, in which R is methyl and R is mononitrosubstituted phenyl.

and 7 mixtures of (l and (2), wherein R is alkyl having a maximum of4 carbon atoms and R is selected from the group consisting of monoand dichlorosubstituted phenyl and mononitrosubstituted phenyl, consisting essentially of reacting an organic isocyanate of the formula RNCO with an azomethine com pound of the formula (CH =NR) wherein x is one of the integers one and three; and R and R are as previously defined, at a temperature below about 50 C. in a molar ratio of the azomethine calculated on the basis of (CH =NR) to isocyanate of approximately 3 to 2, and separating said compound so formed,

7. A process in accordance with claim 1, in which the reaction is in an organic solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons and ethers.

8v A process in accordance with claim 2, in which said or ganic solvent is an aliphatic hydrocarbon and said tempera ture is in the approximate temperature range of 0 to 50 C 9. A process in accordance with claim 3, in which said R is methyl and said aliphatic hydrocarbon is pentane.

10. A process in accordance with claim 7, wherein R is methyl and R is monoor dichlorosubstituted phenyl.

11. A process in accordance with claim 2, wherein R is methyl; R is 3,4-dichlorophenyl; and X is the integer three.

UNITED STATES PATEl i @FFICE CERTIFICATE OF CORRECTIQN Patent No. 5,609,143 Dated September 28, 1971 Inventor(s) J P Chupp It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 1 1, "the" should be and--.

Column 5, line 5%, in the Table identifying the seeds used, "L-Tomato E" should be --L-'I'omato-.

Column 6, line 27, after "three-eighths", insert inch-.

Column 7, line 55, "effect should be effects- Column 9, line 50, that part of the chemical name reading "-gtriazine" should be s s triazine Column 9, line '70, "of" (second occurrence) should be for Line 1 of Claim "claim 7," should be --c1aim l,

Line 1 of Claim 5, "claim 7," should be -claim 1,--.

Line 1 of Claim 7, "claim 1," should be -claim 6,-

Line 1 of Claim 8, "claim 2," should be --claim 7,,

Line 1 of Claim 9, "claim 5," should be --claim 8,-

Line 1 of Claim 11, "claim 2," should be -claim 7,-.

Signed and sealed this 26th day of June 1973.

(SEAL? Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents FORM PO'WSO "$59) USCOMM-DC 50376-P69 Q U 5. GOVERNMENT PRINTNG DFFlCE I969 0-355-334 

2. A compound in accordance with claim 1, in which R is methyl and R'' is mononitrosubstituted phenyl.
 3. A compound in accordance with claim 1, in which R is methyl and R'' is mono- or dichlorosubstituted phenyl.
 4. A compound in accordance with claim 7, in which R is methyl and R'' is 3,4-dichlorophenyl.
 5. A compound in accordance with claim 7, in which R is methyl and R'' is 4-chlorophenyl.
 6. A process for preparing a compound of the formula
 7. A process in accordance with claiM 1, in which the reaction is in an organic solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons and ethers.
 8. A process in accordance with claim 2, in which said organic solvent is an aliphatic hydrocarbon and said temperature is in the approximate temperature range of 0* to 50* C.
 9. A process in accordance with claim 3, in which said R is methyl and said aliphatic hydrocarbon is pentane.
 10. A process in accordance with claim 7, wherein R is methyl and R'' is mono- or dichlorosubstituted phenyl.
 11. A process in accordance with claim 2, wherein R is methyl; R'' is 3,4-dichlorophenyl; and X is the integer three. 